Organic thin-film electronic devices including organic electroluminescent (EL) devices or organic light-emitting devices (OLEDs), organic thin-film photovoltaic devices, and organic thin-film transistors comprise one or more thin-film organic layers most frequently prepared by vacuum deposition. OLEDs, for example, are electronic devices that emit light in response to an applied potential. The structure of a basic OLED includes, in sequence, an anode, an organic EL medium, and a cathode. The organic EL medium disposed between the anode and the cathode is commonly comprised of an organic hole-transporting layer (HTL) and an organic electron-transporting layer (ETL). Holes and electrons recombine and emit light in the ETL near the interface of HTL/ETL. Tang et al., “Organic Electroluminescent Diodes”, Applied Physics Letters, 51, 913 (1987), and commonly assigned U.S. Pat. No. 4,769,292, demonstrated highly efficient OLEDs using such a layer structure. Since then, numerous OLEDs with alternative layer structures have been disclosed. For example, there are three-layer OLEDs that contain an organic light-emitting layer (LEL) between the HTL and the ETL, such as that disclosed by Adachi et al., “Electroluminescence in Organic Films with Three-Layer Structure”, Japanese Journal of Applied Physics, 27, L269 (1988), and by Tang et al., “Electroluminescence of Doped Organic Thin Films”, Journal of Applied Physics, 65, 3610 (1989). The LEL commonly includes a host material doped with a guest material. The HTL and ETL layers can be multi-components. Wherein the layer structures are denoted as HTL/LEL/ETL, Further, there are other multilayer OLEDs that contain a hole-injecting layer (HIL), or an electron-injecting layer (EIL), or a hole-blocking layer, or an electron-blocking layer in the devices. These structures have further resulted in improved device performance.
Moreover, in order to further improve the performance of the OLEDs, an OLED structure called tandem OLED (or stacked OLED), is formed by stacking several individual OLEDs vertically. Forrest et al. in U.S. Pat. No. 5,703,436 and Burrows et al. in U.S. Pat. No. 6,274,980 disclosed their tandem OLEDs. In their inventions, the tandem OLEDs are fabricated by vertically stacking several OLEDs, each independently emitting light of a different color or of the same color. Forrest et al. believed that by using their tandem OLED structure, full color emission devices with higher integrated density in the display can be made. However, each OLED unit in their devices needs a separate power source. In an alternative design, a tandem OLED (or stacked OLED, or cascaded OLED) structure, which is fabricated by stacking several individual OLEDs vertically and driven by only a single power source, was disclosed in (see U.S. Pat. Nos. 6,337,492, 6,107,734, 6,717,358, U.S. Patent Publication Nos. 2003/0170491 A1, 2003/0189401A1, and JP Patent Publication No. 2003045676A). In a tandem OLED having a number of N(N>1) EL units, the luminous efficiency can be N times as high as that of a conventional OLED containing only one EL unit (of course, the drive voltage can also be N times as high as that of the conventional OLED). Therefore, in one aspect to achieve long lifetime, the tandem OLED needs only about 1/N of the current density used in the conventional OLED to obtain the same luminance although the lifetime of the tandem OLED will be about N times that of the conventional OLED. In the other aspect to achieve high luminance, the tandem OLED needs only the same current density used in the conventional OLED to obtain a luminance N times as high as that of the conventional OLED while maintaining about the same lifetime. Each organic EL unit in a tandem OLED is capable of supporting hole and electron-transport, and electron-hole recombination to produce light. Each organic EL unit can comprise a plurality of layers including HTL (hole transport layer), ETL (electron transport layer), LEL (light emitting layer), HIL (hole injection layer), and EIL (electron injection layer). A light-emitting layer (LEL) can comprise one or more sub-layers each emitting a different color. Thus a state-of-the-art OLED device can have a large number of layers. Each of these layers can range from a few nanometer to about a micrometer in thickness and can contain one or more materials. For predictable and reproducible performance, the thickness and the composition of these layers need control.
Physical vapor deposition in a vacuum environment is the principal means of depositing thin organic material films as used in small molecule OLED devices. Such methods are well known, for example Barr in U.S. Pat. No. 2,447,789 and Tanabe et al. in EP 0 982 411. The organic materials used in the manufacture of OLED devices are often subject to degradation when maintained at or near the desired rate dependant vaporization temperature for extended periods of time. Exposure of sensitive organic materials to higher temperatures can cause changes in the structure of the molecules and associated changes in material properties.
To overcome the thermal sensitivity of these materials, only small quantities of organic materials have been loaded in sources and heated as little as possible. In this manner, the material is consumed before it has reached the temperature exposure threshold to cause significant degradation. The limitations with this practice are that the available vaporization rate is very low due to the limitation on heater temperature, and the operation time of the source is very short due to the small quantity of material present in the source. The low deposition rate and frequent source recharging place substantial limitations on the throughput of OLED manufacturing facilities.
A secondary consequence of heating the entire organic material charge to roughly the same temperature is that it is impractical to mix additional organic materials, such as dopants, with a host material unless the vaporization behavior and vapor pressure of the dopant is very close to that of the host material. This is generally not the case and as a result, prior art devices frequently require the use of separate sources to co-deposit host and dopant materials. These multiple sources must be maintained in an angled arrangement so that the evaporated materials from each source converge at a common point on an OLED substrate. This use of multiple spaced-apart sources leads to obvious limitations in the number of materials that can be co-deposited and obvious deficiencies in the homogeneity of the host and dopant films.
The organic materials used in OLED devices have a highly non-linear vaporization-rate dependence on source temperature. A small change in source temperature leads to a very large change in vaporization rate. Despite this, prior art devices employ source temperature as the only means to control vaporization rate. To achieve good temperature control, prior art deposition sources typically utilize heating structures whose solid volume is much larger than the organic charge volume, composed of high thermal-conductivity materials that are well insulated. The high thermal conductivity insures good temperature uniformity through the structure and the large thermal mass helps to maintain the temperature within a critically small range by reducing temperature fluctuations. These measures have the desired effect on steady-state vaporization rate stability but have a detrimental effect at start-up. It is common that these devices must operate for many hours at start-up before steady state thermal equilibrium and hence a steady vaporization rate is achieved.
A further limitation of the prior art is that the geometry of the vapor manifold changes as the organic material charge is consumed. This change requires that the heater temperature change to maintain a constant vaporization rate and it is observed that the plume shape of the vapor exiting the orifices changes as a function of the organic material thickness and distribution in the source.
Furthermore, the prior art cannot be used conveniently to prepare devices that have a large number of layers (more than four or five), in particular if some of these layers are only a few nanometers in thickness. These multilayer structures are needed to achieve the high performance of OLED devices.
Another limitation of the prior art vapor deposition method is the difficulty in controlling the deposition rate and film thickness during the layer deposition process. The most common method uses crystal thickness and rate monitors. The crystals have limited lifetime and cannot easily support extended runs; this method also has limited accuracy especially for materials that have less than perfect sticking coefficients and for layers that are extremely thin.